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Treatment of cylindrospermopsin by hydroxyl and sulfate radicals: Does degradation equal detoxification?
Drinking water treatment ultimately aims to provide safe and harmless drinking water. Therefore, the suitability of a treatment process should not only be assessed based on reducing the concentration os a pollutant concentration but, more importantly, on reducing its toxicity. Hence, the main objective of this study was to answer whether the degradation of a highly toxic compound of global concern for drinking water equals its detoxification. We, therefore, investigated the treatment of cylindrospermopsin (CYN) by •OH and SO4-• produced in Fenton and Fenton-like reactions. Although SO4-• radicals removed the toxin more effectively, both radical species substantially degraded CYN. The underlying degradation mechanisms were similar for both radical species and involved hydroxylation, dehydrogenation, decarboxylation, sulfate group removal, ring cleavage, and further fragmentation. The hydroxymethyl uracil and tricyclic guanidine moieties were the primary targets. Furthermore, the residual toxicity, assessed by a 3-dimensional human in vitro liver model, was substantially reduced during the treatment by both radical species. Although the results indicated that some of the formed degradation products might still be toxic, the overall reduction of the toxicity together with the proposed degradation pathways allowed us to conclude: “Yes, degradation of CYN equals its detoxification!”.
Cylindrospermopsin is effectively degraded in water by pulsed corona-like and dielectric barrier discharges
Cylindrospermopsin (CYN) is an important cyanobacterial toxin posing a major threat to surface waters during cyanobacterial blooms. Hence, methods for cyanotoxin removal are required to confront seasonal or local incidences to sustain the safety of potable water reservoirs. Non-thermal plasmas provide the possibility for an environmentally benign treatment which can be adapted to specific concentrations and environmental conditions without the need of additional chemicals. We therefore investigated the potential of two different non-thermal plasma approaches for CYN degradation, operated either in a water mist, i.e. in air, or submerged in water. A degradation efficacy of 0.03 ± 0.00 g kWh−1 L−1 was found for a dielectric barrier discharge (DBD) operated in air, while a submerged pulsed corona-like discharge resulted in an efficacy of 0.24 ± 0.02 g kWh−1 L−1. CYN degradation followed a pseudo zeroth order or pseudo first order reaction kinetic, respectively. Treatment efficacy of the corona-like discharge submerged in water increased with pH values of the initial solution changing from 5.0 to 7.5. Notably, a pH-depending residual oxidative effect was observed for the submerged discharge, resulting in ongoing CYN degradation, even without further plasma treatment. In this case hydroxyl radicals were identified as the dominant oxidants of CYN at acidic pH values. In comparison, degradation by the DBD could be related primarily to the generation of ozone. © 2020 The AuthorsThe degradation of cylindrospermopsin by a pulsed corona-like discharge in water was more effective compared with a pulsed dielectric barrier discharge in air around a water mist. © 2020 The Authors
Methane emissions from the storage of liquid dairy manure: Influences of season, temperature and storage duration
Methane emissions from livestock manure are primary contributors to GHG emissions from agriculture and options for their mitigation must be found. This paper presents the results of a study on methane emissions from stored liquid dairy cow manure during summer and winter storage periods. Manure from the summer and winter season was stored under controlled conditions in barrels at ambient temperature to simulate manure storage conditions. Methane emissions from the manure samples from the winter season were measured in two time periods: 0 to 69 and 0 to 139 days. For the summer storage period, the experiments covered four time periods: from 0 to 70, 0 to 138, 0 to 209, and 0 to 279 continuous days, with probing every 10 weeks. Additionally, at the end of all storage experiments, samples were placed into eudiometer batch digesters, and their methane emissions were measured at 20 °C for another 60 days to investigate the potential effect of the aging of the liquid manure on its methane emissions. The experiment showed that the methane emissions from manure stored in summer were considerably higher than those from manure stored in winter. CH4 production started after approximately one month, reaching values of 0.061 kg CH4 kg−1 Volatile Solid (VS) and achieving high total emissions of 0.148 kg CH4 kg−1 VS (40 weeks). In winter, the highest emissions level was 0.0011 kg CH4 kg−1 VS (20 weeks). The outcomes of these experimental measurements can be used to suggest strategies for mitigating methane emissions from manure storage.